CN110072925A

CN110072925A - Fenestrated membrane, its manufacturing method and the display device including the fenestrated membrane

Info

Publication number: CN110072925A
Application number: CN201780076606.5A
Authority: CN
Inventors: 韩智映; 朴时均; 申东明; 成洛铉
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2016-12-13
Filing date: 2017-11-03
Publication date: 2019-07-30
Anticipated expiration: 2037-11-03
Also published as: US20200108587A1; US11041057B2; KR20180068252A; CN110072925B; WO2018110830A2; KR102018356B1; WO2018110830A3

Abstract

The present invention provides a kind of fenestrated membrane, its manufacturing method and a kind of display devices including the fenestrated membrane.The fenestrated membrane includes: substrate layer；Window coating is formed on a surface of substrate layer；And back coating, it is formed on another surface of substrate layer, wherein the fenestrated membrane has the relationship of formula 1.

Description

Fenestrated membrane, its manufacturing method and the display device including the fenestrated membrane

Technical field

The present invention relates to a kind of fenestrated membrane, preparation method and a kind of displays including the fenestrated membrane.More specifically, this hair Bright to be related to a kind of fenestrated membrane, which has good optical property (for example, total light transmittance, mist degree and reflectivity), has low Huang Degree has high adherence including between base and back coating in fenestrated membrane, and with high rigidity and flexibility.

Background technique

The outermost of optical display is arranged in fenestrated membrane.Fenestrated membrane includes base and the window coating that is formed in base.Cause This, fenestrated membrane needs to have good transparency and pencil hardness.Fenestrated membrane includes base and the coating that is formed by curable resin.Root According to base and/or curable resin, fenestrated membrane can have high yellowing, and yellow therefore can be presented.In addition, at high temperature Long-term disposal will lead to the high yellowing of fenestrated membrane.

Recently, in display glass substrate or high rigidity substrate envelope substitute, have been developed to fold and The flexible display of expansion.Therefore, fenestrated membrane is also required to have good flexibility.When fenestrated membrane all has low song on two direction When rate radius simultaneously has good flexible therefore, the serviceability of fenestrated membrane can be improved.

Background technique of the invention is disclosed in Korean Patent Publication No. 2011-0087497.

Summary of the invention

[technical problem]

It is an aspect of the invention to provide a kind of fenestrated membranes with high total light transmittance, low haze and antiradar reflectivity.

Another aspect of the present invention is to provide a kind of fenestrated membrane with low yellowing and good appearance.

Another aspect of the present invention is to provide a kind of fenestrated membrane between base and back coating with good adhesiveness.

It is a further aspect of the present invention to provide a kind of fenestrated membrane with high rigidity and high flexibility.

[technical solution]

According to an aspect of the invention, there is provided a kind of fenestrated membrane, comprising: base；Window coating is formed in base On one surface；And back coating, it is formed on another surface of base, wherein the fenestrated membrane meets equation 1:

A¹<A²<A³

(wherein, A¹It is the refractive index of back coating, A²It is the refractive index of window coating, and A³It is the refractive index of base).

According to another aspect of the present invention, a kind of method for preparing fenestrated membrane is provided, comprising: exist using back coating composition Back coating is formed on one surface of base；And window painting is formed on another surface of base using window coating composition Layer, wherein the back coating composition includes: inorganic hollow particle；At least one of fluorochemical monomer and its oligomer；It is floride-free single At least one of body and its oligomer；Initiator；Dyestuff；And solvent.

According to another aspect of the present invention, a kind of display including above-mentioned fenestrated membrane is provided.

[advantageous effects]

The present invention provides a kind of fenestrated membrane with high total light transmittance, low haze and antiradar reflectivity.

The present invention provides a kind of fenestrated membrane with low yellowing and good appearance.

The present invention provides a kind of fenestrated membrane between base and back coating with good adhesiveness.

The present invention provides a kind of fenestrated membrane with high rigidity and high flexibility.

Detailed description of the invention

Fig. 1 is the cross-sectional view of fenestrated membrane according to an embodiment of the invention；

Fig. 2 is the cross-sectional view of fenestrated membrane according to another embodiment of the present invention；

Fig. 3 is the cross-sectional view of flexible display according to an embodiment of the invention；

Fig. 4 is the cross-sectional view of one embodiment of display portion shown in Fig. 3；

Fig. 5 is the cross-sectional view of flexible display according to another embodiment of the present invention；

Fig. 6 is the cross-sectional view of flexible display according to another embodiment of the present invention.

Specific embodiment

The embodiment of the present invention will be described in detail with reference to the attached drawings.It should be appreciated that the present invention can be implemented in different ways, And it is not limited to following embodiment.In the accompanying drawings, for the sake of clarity, the part unrelated with description will be omitted.Entirely illustrating In book, identical component will be indicated by the same numbers.

As used herein, with reference to attached drawing definition space relative terms, for example, "up" and "down".It will thus be appreciated that art Language " upper surface " can be used interchangeably with term " lower surface ".It is arranged on another element or layer when an element or layer are referred to as When, the element or layer can be arranged directly on another element or layer, or may exist intermediary element or layer.However, when one When a element or layer referred to as " are set up directly on " on another element or layer, intermediary element or layer is not present.

As used herein, " ultraviolet-curing group " refers to: epoxy group；(methyl) acrylate group；(methyl) Acrylamide group；Vinyl；Cycloaliphatic epoxy groups；Glycidoxypropyl；Oxetane groups；Or contain epoxy group, (first Base) acrylate-based, (methyl) acrylamido, vinyl, alicyclic epoxy group, glycidoxypropyl or oxetanyl C₁To C₆Alkyl or C₅To C1₀Naphthenic base.Here, cycloaliphatic epoxy groups refer to epoxidised C₄To C₁₀Group of naphthene base, " Ec " indicates that (3,4- epoxycyclohexyl) ethyl, " Gp " indicate that 3- glycidyl-oxypropyl, " Op " indicate 3- oxetanylmethoxy third Base, " Me " indicates methyl, and " Et " indicates ethyl.

As used herein, term " (methyl) acrylic acid " refers to acrylic acid and/or methacrylic acid.In addition, unless otherwise Illustrate, term " substitution " refers at least one hydrogen atom in functional group by hydroxyl, unsubstituted C₁To C₁₀Alkyl, C₁To C₁₀Alkane Oxygroup, C₃To C₁₀Naphthenic base, C₆To C₂₀Aryl, C₇To C₂₀Aryl alkyl, benzophenone base, by C₁To C₁₀Alkyl-substituted C₆Extremely C₂₀Aryl or by C₁To C₁₀The C that alkoxy replaces₁To C₁₀Alkyl replaces.As used herein, " halogen " refers to fluorine, chlorine, bromine or iodine.

As used herein, " refractive index " is the value measured using ellipsometer (J.A.Woollam).

As used herein, " yellow colour index " is the value measured according to ASTM D1925.

As used herein, " reflectivity " is the value according to 8722 canonical measure of ASTM E1164 and JIS Z.

Hereinafter, fenestrated membrane according to an embodiment of the invention will be described with reference to Fig. 1.Fig. 1 is according to the present invention The cross-sectional view of the fenestrated membrane of one embodiment.

With reference to Fig. 1, fenestrated membrane 100 includes base 110, window coating 120 and back coating 130 according to this embodiment, and It can satisfy equation 1:

A¹<A²<A³

When meeting equation 1, fenestrated membrane 100 can have high total light transmittance, low haze and antiradar reflectivity.Particularly, when Fenestrated membrane 100 include the back coating 130 on the lower surface of base 110 and the window coating on the upper surface of base 110 120 simultaneously And when meeting equation 1, fenestrated membrane 100 can have the interior lights for passing through back coating 130, base 110 and window coating 120 high saturating Penetrate rate.Further, since back coating 130 has than base 110 and the lower refractive index of window coating 120, fenestrated membrane 100 can be external Portion's light has antiradar reflectivity.

Specifically, when the measurement in the visibility region (for example, under 380 nanometers to 800 nanometers wavelength), fenestrated membrane can be with Total light transmittance with 90% or bigger, particularly 91% or bigger (for example, 91% to 100%).In addition, when in visibility region In (for example, under 380 nanometers to 800 nanometers wavelength) when measurement, fenestrated membrane can have 2% or smaller mist degree, especially 0.1% to 2% mist degree.In addition, the reflectivity of fenestrated membrane is 8% or lower, especially 7% or lower or 6.8% or lower, example Such as, 0% to 7.1%.Within the scope of these, when in the display in use, the display quality of display can be improved in fenestrated membrane.

In one embodiment, fenestrated membrane may include polyimide film, as base.In general, polyimide film can have There are 3 or bigger yellow colour index, for example, 3 to 9.Although, as base, fenestrated membrane can have including polyimide film The total light transmittance of 90% or bigger (for example, 90% to 99%) for being measured in visible light region, 8% or smaller (especially 7% or It is smaller) or 6.8% or smaller (for example, 0% to 7.1%) reflectivity, 2.3 or smaller (for example, 0 to 2.3) yellow colour index. Within the scope of these, when in the display in use, the display quality of display can be improved in fenestrated membrane.

In another embodiment, fenestrated membrane may include polyimide film, and as base, and window coating may include silicon Resin.Also in this case, fenestrated membrane can have 90% measured in visibility region or bigger by (especially 91% or more Greatly, for example, 91% to 100%) total light transmittance, 8% or smaller (especially 7% or smaller or 6.8% or smaller, for example, 0% to 7.1%) reflectivity and 2.3% or smaller (for example, 0 to 2.3) yellow chromaticity.Within the scope of these, when showing In use, the picture quality of display can be improved in fenestrated membrane in device.

Base

Base 110 can increase the mechanical strength of fenestrated membrane 100 by support fenestrated membrane 100.Although base 110 can be with right and wrong Flexible membrane, but flexible membrane may be used as base 110, to improve the flexibility of fenestrated membrane 100.

In one embodiment, base can have 1.60 or higher refractive index, for example, 1.60 to 1.75.In the model In enclosing, fenestrated membrane can easily meet equation 1, and can be due between base and each of window coating and back coating Refractive index difference and increase transmissivity and reduce reflectivity.

In one embodiment, base 110 can have 3 or bigger yellow colour index, for example, 3 to 9.When fenestrated membrane 100 wraps Including yellow colour index is 3 or higher base 110 and when meeting equation 1, and fenestrated membrane 100 can have high total light transmittance and low anti- Penetrate rate.

Base 110 can be formed by optical clear resin.Specifically, optical clear resin may include polyester resin (example Such as, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT) and poly- naphthalenedicarboxylic acid fourth Diol ester), polycarbonate resin, poly- (methyl) acrylate (for example, poly- (methyl methacrylate)), polystyrene tree At least one of rouge, polyamide, polyimide resin and cyclic olefin polymer.Preferably, base 110 is by polyamides Asia The film that polyimide resin is formed.Therefore, base 110 has high-fire resistance, and therefore can increase the heat resistance of fenestrated membrane 100.

Base 110 can have the thickness of 10 μm to 150 μm (especially 30 μm of m to 100 μm of m).In the range, base It can be used in fenestrated membrane.

In Fig. 1, base is shown as formed in single layer.It will be appreciated, however, that the invention is not limited thereto, and base It can be formed as multilayer.For example, base can be pellicular cascade, wherein the first base, adhesive phase and the second base are with described Sequence stacks, wherein the first base and the second base can be via clear binder (for example, optically clear adhesives (OCA)) It is bonded to each other.The type of OCA is not particularly limited.Each of first base and the second base can be above-mentioned base.The The thickness and material of one base can be identical or different with the thickness and material of the second base.The total light transmittance of OCA is up to 90% Or it is bigger.In the range, the first base can be adhered to the second base by OCA, the performance without influencing fenestrated membrane.For example, OCA It can be formed by adhesive phase composition, which includes: (methyl) acrylic copolymer for hydroxyl Monomer mixture；Initiator；And at least one of macromonomer and organic nanometer granule.Here, monomer mixes Object can (methyl) acrylate by (methyl) acrylate of hydroxyl and containing alkyl form.Organic nanometer granule is nucleocapsid Type particle, and can satisfy equation 2:

Tg(c)<Tg(s)

(wherein, Tg (c) is the glass transition temperature (unit: DEG C) of core, and Tg (s) is the glass transition temperature of shell Degree (unit: DEG C).Organic nanometer granule can have 10 nanometers to 400 nanometers, particularly 10 nanometers to 300 nanometers, particularly It is the average grain diameter of 30 nanometers to 280 nanometers, still more particularly 50 nanometers to 280 nanometers.In the range, in visibility region When measurement, adhesive phase can have 90% or bigger total light transmittance, and therefore can have good transparency, without Influence the folding of fenestrated membrane.Core can have -150 DEG C to 10 DEG C, specifically -150 DEG C to -5 DEG C, more specifically -150 DEG C to -20 DEG C glass transition temperature.In the range, adhesive phase can have viscoplasticity in low temperature and/or at room temperature.Core can be with Including at least one of poly- alkyl (methyl) acrylate, polysiloxanes and polybutadiene.Shell can have 15 DEG C to 150 DEG C, particularly 35 DEG C to 150 DEG C, more particularly 50 DEG C to 140 DEG C of glass transition temperature.In the range, organic nano Particle can have good dispersibility in (methyl) acrylic copolymer.Shell may include alkyl methacrylate polymer Ester.

Window coating

Window coating 120 is formed on a surface of base 110, to ensure the optical property of fenestrated membrane 100, for example, thoroughly Rate or mist degree are penetrated, and improves the pencil hardness and flexibility of fenestrated membrane 100, to allow fenestrated membrane for flexible display and non-flexible In display.Window coating 120 can be formed directly into base 110.Here, statement " being formed directly into above " is indicated in window There is no intermediary adhesive layer etc. between mouth coating 120 and base 110.The interior lights of reference display, window coating 120 can be with shapes At on the light exit surface of base 110.

Window coating 120 can have the refractive index less than 1.60, for example, 1.53 to 1.59.In the range, fenestrated membrane can Easily to meet equation 1, and due to the refractive index difference between window coating and base, high-transmission rate and low can have Reflectivity.

Window coating 120 can have 5 μm to 150 μm, particularly 5 μm to 100 μm, more particularly 5 μm to 80 μm or 5 μm To 50 μm of thickness.In the range, fenestrated membrane can have good flexibility.

Window coating 120 can be by including that the window coating composition of silicone resin is formed.Therefore, window coating composition can To realize the fenestrated membrane with high pencil hardness and good flexibility.Window coating composition may include silicone resin, curable monomer And initiator.Now, it will be described in window coating composition.

Silicone resin forms the matrix of window coating 120, and can increase the flexibility and pencil hardness of fenestrated membrane 100.Silicon tree Rouge may include the silicone resin of the group containing ultraviolet curing.The silicone resin of the curing groups containing ultraviolet light may include by The silicone resin that formula 1 indicates:

(R¹SiO_3/2)_x(R²SiO_3/2)_y(R³R⁴SiO_2/2)_z

(wherein, R¹And R²It is independently ultraviolet-curing group, and R¹And R²It is different from each other,

R³And R⁴It is independently hydrogen, ultraviolet-curing group, unsubstituted or substituted C₁To C₂₀Alkyl is unsubstituted Or the C replaced₅To C₂₀Naphthenic base, and x, y and z are set to satisfaction 0 < x≤1,0≤y < 1,0≤z < 1 and x+y+z=1).

R¹And R²Cross linkable is provided, and can contain alicyclic epoxy group, glycidoxypropyl or oxa- The C of cyclobutane group₁To C₆Alkyl or C₅To C₁₀Naphthenic base, more specifically, (3,4- epoxycyclohexyl) methyl, (3,4- epoxide rings Hexyl) ethyl, (3,4- epoxycyclohexyl) propyl, 3- glycidyl-oxypropyl, 3- oxetanes methyl, 3- oxetanes Ethyl or 3- oxetanes propyl.

R³And R⁴Bridging property and flexibility further are provided for window coating 120, and can contain aliphatic ring The C of oxygroup, glycidoxypropyl or oxetanyl₁To C₆Alkyl or C₅To C₁₀Naphthenic base or unsubstituted or substituted C₁Extremely C₁₀Alkyl, more specifically, (3,4- epoxycyclohexyl) methyl, (3,4- epoxycyclohexyl) ethyl, (3,4- epoxycyclohexyl) third Base, glycidoxypropyl, methyl or ethyl.

In one embodiment, the silicone resin of the group containing ultraviolet curing can be any into 1-3 by formula 1-1 The silicone resin of a expression:

R¹SiO_3/2

(R¹SiO_3/2)_x(R²SiO_3/2)_y

(R¹SiO_3/2)_x(R³R⁴SiO_2/2)_z

In formula 1-1 into 1-3, R¹、R²、R³And R⁴As defined in formula 1, and x, y and z be set as 0 < x of satisfaction < 1,0 < y < 1,0 < z < 1, x+y=1 and x+z=1.Specifically, x, y and z may be configured as satisfaction 0.20≤x≤0.999,0.001≤y ≤ 0.80 and 0.001≤z≤0.80, more specifically, meet 0.20≤x≤0.99,0.01≤y≤0.80 and 0.01≤z≤ 0.80, more specifically, meeting 0.50≤x≤0.99,0.01≤y≤0.50 and 0.01≤z≤0.50, more specifically, 0.90≤x ≤0.97,0.03≤y≤0.10,0.03≤z≤0.10.In the range, fenestrated membrane can have good pencil hardness and soft Property.Specifically, silicone resin may include by EcSiO_3/2Expression T unit composition silicone resin and by GpSiO_3/2Table At least one of the silicone resin of the T unit composition shown.In addition, silicone resin can be including (EcSiO_3/2)_x (GpSiO_3/2)_yThe silicone resin of (0 < x < 1,0 < y < 1, x+y=1).In addition, silicone resin can include but is not limited to public affairs Any one of formula 1-3A to 1-3L:

(EcSiO_3/2)_x((Me)₂SiO_2/2)_z

(EcSiO_3/2)_x(MeEtSiO_2/2)_z

(GpSiO_3/2)_x((Me)₂SiO_2/2)_z

(GpSiO_3/2)_x(MeEtSiO_2/2)_z

(OpSiO_3/2)_x((Me)₂SiO_2/2)_z

(OpSiO_3/2)_x(MeEtSiO_2/2)_z

(EcSiO_3/2)_x(EcMeSiO_2/2)_z

(EcSiO_3/2)_x(GpMeSiO_2/2)_z

(GpSiO_3/2)_x(EcMeSiO_2/2)_z

(GpSiO_3/2)_x(GpMeSiO_2/2)_z

(OpSiO_3/2)_x(EcMeSiO_2/2)_z

(OpSiO_3/2)_x(GpMeSiO_2/2)_z

(wherein, x, y and z are set as satisfaction 0 < x < 1,0 < z < 1 and x+z=1).

The weight average molecular weight of the silicone resin of the group containing ultraviolet curing can be 1,000g/mol to 15,000g/ Mol, for example, 4,000g/mol to 8,000g/mol.The polydispersity index (PDI) of the silicone resin of the curing groups containing ultraviolet light It can be 1.0 to 3.0.When the weight average molecular weight and polydispersity index of the silicone resin of the curing groups containing ultraviolet light fall in these When in range, due to the close cross-linked network of silicone resin, fenestrated membrane can have high pencil hardness and transparency.

The silicone resin of the group containing ultraviolet curing indicated by formula 1 can be by being provided separately R¹SiO_3/2Alkane Oxysilane or including provide R¹SiO_3/2Alkoxy silane, provide R²SiO_3/2Alkoxy silane and provide R³R⁴SiO_2/2's It is prepared by the hydrolysis and condensation of the monomer mixture of at least one of alkoxy silane.Hydrolysis and condensation are those skilled in the art Member is well-known.Specifically, hydrolysis and condensation can carry out at room temperature 12 hours to 7 days, or can be at 60 DEG C to 100 It is carried out 2 hours to 72 hours at DEG C, to promote to react, but not limited to this.Although to the curing groups containing ultraviolet light are used to prepare The solvent of silicone resin is not particularly limited, but the solvent may include water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just At least one of butanol, the tert-butyl alcohol and methoxypropanol.In hydrolysis and condensation, catalyst can be further used to control Reaction rate.The example of catalyst may include: acid catalyst, for example, hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric acid, chlorosulfonic acid Or acid iodide；Basic catalyst, for example, ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide and imidazoles；And ion exchange resin, For example, Amberite IRA-400 or IRA-67.

In addition, the silicone resin of the group containing ultraviolet curing can include but is not limited to by individually being indicated by formula 2 Compound or the compound that is indicated by formula 2 and the compound indicated by formula 3 mixture hydrolysis and condensation preparation Silicone resin:

R⁵-R⁸-Si(OR⁶)_m(R⁷)_3-m

(wherein, R⁵It is ultraviolet-curing group, R⁶It is C₁To C₁₀Alkyl, R⁷It is C₁To C₁₀Alkyl, C₃To C₂₀Naphthenic base, C₆To C₂₀Aryl or C₇To C₂₀Aryl alkyl, R⁸It is singly-bound or C₁To C₁₀Alkylidene, and m is integer of 1 to 3),

Si(OR⁹)_n(R¹⁰)_4-n

(wherein, R⁹It is C₁To C₁₀Alkyl, R¹⁰It is unsubstituted C₁To C₂₀Alkyl, C₃To C₈Naphthenic base, C₃To C₂₀Alkenyl, C₂ To C₂₀Alkynyl, C₆To C₂₀Aryl, halogen, halogen-containing C₁To C₁₀Alkyl, amino, amino-containing C₁To C₁₀Alkyl, sulfydryl, C₁Extremely C₁₀Ether, carbonyl, carboxylic acid group or nitro, and n is 1 to 4 integer).

In formula 2, term " singly-bound " refers to R⁵Directly it is connected with Si, without R⁸.Specifically, the chemical combination indicated by formula 2 Object can be 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl triethoxy silicane Alkane, (methyl) propenyloxy group propyl trimethoxy silicane, (methyl) propenyloxy group propyl-triethoxysilicane and vinyl front three At least one of oxysilane, but not limited to this.

It specifically, may include tetramethoxy-silicane, tetraethoxysilane, methyl trimethoxy by the compound that formula 3 indicates Oxysilane, methyltriethoxysilane, methyl tripropoxy silane, dimethyldimethoxysil,ne, dimethyl diethoxy Silane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, diphenyl diethoxy silane, triphenylmethoxy silane, Triphenyl Ethoxysilane, ethyl triethoxysilane, ethyl trimethoxy silane, 3- aminopropyl trimethoxy silicon At least one of alkane, 3-aminopropyltriethoxysilane, r-chloropropyl trimethoxyl silane and chloropropyl triethoxysilane.

Curable monomer increases the pencil hardness of fenestrated membrane by being crosslinked with silicone resin, and passes through control window coating group The viscosity of object is closed to provide good processing performance.Curable monomer may include monomer containing epoxy group, containing anhydride group Monomer and at least one of the monomer of oxetane group-containing.Monomer containing epoxy group may include containing at least one The photo-curing monomer of a epoxy group.Here, epoxy group may include epoxy group and the organic group containing epoxy group, For example, glycidyl.Monomer containing epoxy group may include cycloaliphatic epoxy monomer, aromatics epoxy monomer, aliphatic epoxy Or mixtures thereof monomer, hydrogenated epoxy monomer.Cycloaliphatic epoxy monomer is in C₃To C₁₀There is at least one ring in aliphatic ring The monomer of oxygen groups, and can be such as 3,4- epoxycyclohexyl-methyl -3', 4'- epoxycyclohexyl formic acid esters, but be not limited to This.Aromatics epoxy monomer can be bisphenol-A, Bisphenol F, phenol novolacs, cresol novolak, triphenylmenthane glycidol Ether, four glycidol methylene dianiline (MDA)s etc..Aliphatic epoxy monomer can be 1,4- butanediol diglycidyl ether, 1,6- oneself Hexanediol diglycidyl ether etc..Hydrogenated epoxy monomer is obtained by Hydrogenated aromatic epoxy monomer, and can be hydrogenated bisphenol A Diglycidyl ether etc..Monomer containing anhydride group may include phthalic anhydride, tetrabydrophthalic anhydride, hexahydro neighbour's benzene At least one of dicarboxylic acid anhydride, Na Dike methyl anhydride, chlorendic anhydride and pyromellitic dianhydride.Oxetane group-containing Monomer may include 3- methy oxetane, 2- methy oxetane, 3- oxetanes, 2- methylene oxa- ring fourth Alkane, 3,3- oxetanes diformazan mercaptan, 4- (3- methy oxetane -3- base) benzonitrile, N- (2,2- dimethyl propyl) -3- Methyl -3- oxetanes methylamine, N- (1,2- dimethylbutyl) -3- methyl -3- oxetanes methylamine, (3- ethyl oxa- Cyclobutane -3- base) methyl (methyl) acrylate, 3- ethyl -3- hydroxymethyl-oxetane, 2- Ethyloxetane, two In toluene dioxygen azetidine and 3- ethyl -3- [[(3- Ethyloxetane -3- base) methoxyl group) methyl] oxetanes At least one.

Initiator is used for constitutes of silicones and curable monomer, to form window coating.Initiator may include photoion Initiator, cationic at least one of thermal polymerization and optical free radical initiator.

Photoion initiator generates cation when light irradiates, and to promote to solidify, and may include known in the art Any suitable photoion initiator.Specifically, photoion initiator may include cationic salts and anion salt.Cation Example may include: Diaryl iodonium, for example, diphenyl iodine, 4- methoxyl group diphenyl iodine, bis- (4- aminomethyl phenyl) iodine , (4- aminomethyl phenyl) [(4- (2- methyl-propyl) phenyl) iodine], bis- (4- tert-butyl-phenyl) iodine, bis- (detergent alkylates Base) iodine and bis- (dodecylphenyl) iodine；Triaryl matte, for example, triphenylsulfonium, diphenyl -4- thienyl phenyl sulfonium；It is double [4- (diazodisulfones) phenyl] sulfide；Bis- [4- (two (4- (2- ethoxy) phenyl) sulfonyls)-phenyl] sulfide；With And (η 5-2,4- cyclopentadiene -1- base) [(1,2,3,4,5,6- η)-(1- Methylethyl) benzene] iron (1⁺).The example of anion can To include tetrafluoroborate (BF₄ ^-), hexafluorophosphate (PF₆ ^-), hexafluoro antimonate (SbF₆ ^-), hexafluoro arsenate (AsF₆ ^-) and six The anti-mono-acid salt (SbCl of chlorine₆ ^-).The example of cationic thermal polymerization may include 3- methyl-2-butene base tetramethyl sulfone, ytterbium, Samarium, erbium, dysprosium, lanthanum, 4-butyl-phosphonium, Yi base triphenyl phosphonium bromide salt, benzyldimethylamine, 2,4, dimethylaminomethyl phenol, three Ethanol amine, N- butylimidazolium and 2-ethyl-4-methylimidazole.The example of anion may include tetrafluoroborate (BF₄ ^-), six Fluorophosphate (PF₆ ^-), hexafluoro antimonate (SbF₆ ^-), hexafluoro arsenate (AsF₆ ^-) and the anti-mono-acid salt (SbCl of chlordene₆ ^-).Light is free Base initiator generates free radical when light irradiates, and to promote to solidify, and may include any suitable light known in the art Radical initiator.Specifically, optical free radical initiator may include phosphorus, triazine, acetophenone, benzophenone, thioxanthones, benzene idol At least one of relation by marriage, oxime and phenyl ketone optical free radical initiator.

When measuring at 25 DEG C, window coating composition can have the viscosity of 1cP to 3,000cP.In the range, Window coating composition can have it is good can coating and applicability, and therefore can be readily formed window coating It is interior.

With solid content meter, window coating composition may include the silicone resin of 65wt% to 95wt%, 4wt% extremely The curable monomer and 0.1wt% of 30wt% to 10wt% initiator.In the range, window coating can have high flexibility With high pencil hardness.As used herein, term " solid content " refers to the content of all solids substance in addition to the solvents.

With solid content meter, window coating composition may include the silicone resin of 100 parts by weight, 1 parts by weight to 20 weight Part, particularly 1 parts by weight to 15 parts by weight, the curable monomer of more particularly 10 parts by weight to 15 parts by weight and 0.1 parts by weight To the initiator of 20 parts by weight, particularly 0.5 parts by weight to 10 parts by weight.In the range, window coating can have Gao Rou Property and high pencil hardness.

Window coating composition can also include any typical additive known in the art.Additive may include resist it is quiet At least one of electric agent, levelling agent, antioxidant, stabilizer and colorant.

Window coating composition can also include solvent, for example, methyl ethyl ketone.

Window coating composition can also include nano particle.The pencil that nano particle can be further improved fenestrated membrane is hard Degree.Nano particle may include at least one of silica, aluminium oxide, zirconium oxide and titanium oxide, but not limited to this.Nanometer Particle can be surface-treated with silicone compounds, and be not limited to specific shape or size.Specifically, nano particle can To have spherical, sheet or amorphous granular shape.Nano particle can have 1 nanometer to 200 nanometers, particularly 5 nanometers extremely 50 nanometers, more particularly 10 nanometers to 30 nanometers of average particle size (D50).In the range, nano particle can increase fenestrated membrane Pencil hardness, without influence window coating surface roughness and transparency.With solid content meter, relative to 100 parts by weight Silicone resin, the amount of nano particle can be 0.1 parts by weight to 100 parts by weight, particularly from about 1 parts by weight to 80 weight Part.In the range, nano particle can increase the pencil hardness of fenestrated membrane, while reduce the surface roughness of window coating.

Back coating

Back coating 130 is formed on another surface of base 110, to support fenestrated membrane 100.In Fig. 1, back coating 110 is aobvious It is shown as being formed directly into base 110.Herein, statement " being formed directly into above " is indicated in back coating 130 and base 110 Between there is no intermediary adhesive layer.The interior lights of reference display, the light that back coating 130 can be formed in base 110 enter firing table On face.

Back coating 130 can have 1.54 or smaller refractive index, for example, 1.39 to 1.54 or 1.39 to 1.52.At this In range, fenestrated membrane can easily meet equation 1, and due to the refractive index difference between coating and base, can have height Transmissivity and antiradar reflectivity.

Back coating 130 may include inorganic hollow particle, fluorochemical monomer or at least one of its oligomer and dyestuff. Preferably, back coating includes: inorganic hollow particle；Fluorochemical monomer or its oligomer；And at least one of dyestuff.Therefore, Back coating has the refractive index lower than base and window coating, and can reduce the yellowing of fenestrated membrane.

Back coating may include the inorganic hollow particle and fluorochemical monomer or its oligomer of 9wt% to 80wt% in total.? Within the scope of this, since the refractive index between coating and base is different, fenestrated membrane can have high-transmission rate and antiradar reflectivity.Back coating It may include 9wt% to 80wt%, for example, 9wt% is to the fluorochemical monomer of 78wt% or its oligomer.In the range, due to Refractive index difference between coating and base, fenestrated membrane can have high-transmission rate, antiradar reflectivity and low yellowing.

In one embodiment, back coating can be formed by back coating composition, and the composition includes: inorganic hollow Grain；At least one of fluorochemical monomer and its oligomer；Fluorine-free monomer or its oligomer；Initiator；And dyestuff.

The refractive index of inorganic hollow particle can be 1.4 or lower, specifically for 1.33 to 1.38.Inorganic hollow particle can be with Average grain diameter (D50) with 30 nanometers to 100 nanometers, especially 40 nanometer to 70 nanometers.In the range, inorganic hollow Grain may be embodied in back coating, and can be advantageously applied for fenestrated membrane.Inorganic hollow particle may include silica, not Come stone, aluminium oxide, silicon carbide (SiC), MgO-Al₂O₃-SiO₂、Al₂O₃-SiO₂、MgO-Al₂O₃-SiO₂-LiO₂Or mixtures thereof, It is all these to can be carried out being surface-treated.Preferably, inorganic hollow particle may include hollow silica.

Fluorochemical monomer or its oligomer may include fluorine-containing (methyl) acrylic monomers or its oligomer.

Can in the form of their own comprising inorganic hollow particle and fluorochemical monomer or its oligomer, or can with comprising The form of the solution of all these components includes.The solution can also include initiator, (methyl) acrylic monomers and solvent, example Such as, methyl iso-butyl ketone (MIBK).The entirety of inorganic hollow particle and fluorochemical monomer or its oligomer or comprising inorganic hollow particle and The whole solution of fluorochemical monomer or its oligomer can have the refractive index of 1.42 or smaller (especially 1.33 to 1.38).? Within the scope of this, the refractive index of back coating can be reduced.The solution may include any suitable commercial product, for example, XJA- 0247 (Pelnox company), but not limited to this.

With solid content meter, the total amount of inorganic hollow particle and fluorochemical monomer or its oligomer in back coating composition can Think 9wt% to 80wt%, especially 9wt% to 78wt%.In the range, not due to the refractive index between coating and base Together, fenestrated membrane can have high-transmission rate, antiradar reflectivity and low yellowing.

Preferably, fluorine-free monomer or its oligomer are groups containing ultraviolet curing (for example, acrylate-based containing (methyl) Group or epoxy group) compound.Fluorine-free monomer or its oligomer may include multifunctional (methyl) acrylate monomer and its At least one of oligomer.Fluorine-free monomer or its oligomer can be difunctionality to ten functions (methyl) acrylate chemical combination Object.

Fluorine-free monomer or its oligomer may include multifunctional (methyl) acrylate (for example, polyalcohol and (methyl) third The ester of olefin(e) acid or polyfunctional carbamate (methyl) acrylate by polyols preparation), isocyanate compound and (first Base) acrylic acid at least one of hydroxy ester.Preferably, fluorine-free monomer or its oligomer include difunctionality or higher functional (methyl) acrylic monomers, it is highly preferred that trifunctional is to six functions (methyl) acrylic monomers.These can be used alone or mix It closes and uses.

Floride-free (methyl) acrylate oligomer may include (methyl) acrylate oligomers of difunctionality or higher functional Object, especially (methyl) acrylate oligomer of difunctionality to six functions.Preferably, floride-free (methyl) acrylate oligomer It may include carbamate (methyl) acrylate oligomer.Carbamate (methyl) acrylic acid oligomer, which can be, to be passed through Any typical method known in the art contains at least one polyalcohol, at least one polyisocyanate compound and at least one (methyl) acrylate of hydroxyl carries out urethane and carbamate (methyl) acrylic acid oligomer for preparing.Herein Place, polyalcohol may include aromatic polyether polyalcohol, aliphatic poly ethoxylated polyhydric alcohol, alicyclic polyether polyol, polyester polyols At least one of alcohol, polycarbonate polyol and polycaprolactone polyol.Polyisocyanate compound is that have at least two The compound of isocyanate groups, and its example may include that toluene di-isocyanate(TDI), xylene diisocyanate, naphthalene two are different Cyanate, phenylene vulcabond, methyl diphenylene diisocyanate, sub- biphenyl diisocyanate, hexane diisocyanate, Isophorone diisocyanate or its adduct.(methyl) acrylate of hydroxyl is the C at least one hydroxyl₁To C₁₀ (methyl) acrylate, and its example may include 2- ethoxy and (methyl) acrylic acid and 1,4-butanediol (methyl) propylene Acid.Specifically, carbamate (methyl) acrylic acid oligomer may include six functional aliphatic's carbamates (methyl) third Olefin(e) acid oligomer.The weight average molecular weight of floride-free (methyl) acrylate oligomer can be 500g/mol to 8000g/mol, especially It is 1000g/mol to 5000g/mol.In the range, fenestrated membrane can have high pencil hardness and good flexibility.

Fluorine-free monomer can be (methyl) acrylate of difunctionality or higher functional.

The example of bifunctional (methyl) acrylate may include ethylene glycol two (methyl) acrylate, two (first of diethylene glycol (DEG) Base) acrylate, butanediol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, nonane glycol two (methyl) third Olefin(e) acid ester, ethoxylation hexylene glycol two (methyl) acrylate, propoxylation hexylene glycol two (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, glycol polypropylene Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate and Tripropylene glycol two (methyl) acrylate.

The example of trifunctional or higher functional (methyl) acrylate may include: trifunctional (methyl) acrylate, example Such as, trimethylolpropane tris (methyl) acrylate, three -2- hydroxyethylisocyanurate three (methyl) acrylate, glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, (methyl) acrylate of dipentaerythritol three and two or three hydroxyl first Base propane three (methyl) acrylate；Alkoxy-modified trifunctional (methyl) acrylate, for example, ethoxylation trihydroxy methyl Propane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, propoxylation trihydroxy methyl third Alkane three (methyl) acrylate, propoxylated glycerol three (methyl) acrylate；Tetrafunctional (methyl) acrylate, for example, season Penta tetrol four (methyl) acrylate, two trimethylolpropanes, four (methyl) acrylate and dipentaerythritol four (methyl) propylene Acid esters；Five functions (methyl) acrylate, for example, five (first of (methyl) acrylate of pentaerythrite five and two trimethylolpropanes Base) acrylate；And six function (methyl) acrylate, for example, dipentaerythritol six (methyl) acrylate and two or three hydroxyls Methylpropane six (methyl) acrylate.

With solid content meter, the content of fluorine-free monomer or its oligomer in back coating composition can be for 15wt% extremely 88wt%, especially 19wt% are to 87wt%.In the range, since the refractive index between coating and base is different, fenestrated membrane can With high-transmission rate, antiradar reflectivity and low yellowing.

Initiator be can have 150 nanometers to 500 nanometers absorbing wavelength Photoepolymerizationinitiater initiater, and may include α-hydroxyl At least one of base ketone initiator and α-aminoketone initiator, for example, 1- hydroxycyclohexylphenylketone or the mixing including it Object.

With solid content meter, content of the initiator in back coating composition can be 1wt% to 5wt%, especially 1wt% to 3wt%.In the range, the solid matter in back coating composition can be fully cured, and can prevent due to The deterioration of fenestrated membrane optical property caused by the residual of initiator.

Dyestuff be used for by reduce fenestrated membrane yellowing come prevent fenestrated membrane present yellow, without make base, window coating and The optical performance degradation of fenestrated membrane.Dyestuff can have the maximum of 500 nanometers to 650 nanometers (especially 550 nanometers to 620 nanometers) Absorbing wavelength.In the range, dyestuff can reduce the yellowing of fenestrated membrane, without making base, window coating and the optics of fenestrated membrane Performance deterioration.As used herein, term " maximum absorption wavelength " refers to the wavelength corresponding to maximum absorption band, that is, corresponds to wave The wavelength of absorption maximum on long correlation absorption curve.For example, dyestuff may include in metal dye and nonmetallic dyestuff extremely Few one kind, they all have 500 nanometers to 650 nanometers of maximum absorption wavelength.Metal dye may include maximum absorption wavelength For 500 nanometers to 650 nanometers (especially 550 nanometers to 620 nanometers) and wrap metalliferous dyestuff.Specifically, metal dye It may include at least one metal complex, for example, vanadium, chromium and manganese complex, but not limited to this.For example, metal dye can be with It is conjugation heterocycle vanudium complex.Nonmetallic dyestuff may include without metal and a length of 500 nanometers to 650 of maximum absorption wave are received The dyestuff of rice (especially 550 nanometers to 620 nanometers).Specifically, nonmetallic dyestuff may include cyanine dyes, porphyrin (for example, four Aza porphyrin), arylmethane, Fang Fangji, azo methine, oxo alcohol, azo, arlydene, in xanthene and portion's cyanine dyes extremely Few one kind, but not limited to this.For example, dyestuff may include KCF indigo plant b (Kyung-In Synthetic, maximum absorption wavelength: 596 Nanometer, tetraazatetradecane porphyrin dyestuff), SK-D584 (SK Chemicals, maximum absorption wavelength: 584 nanometers, tetraazatetradecane porphyrin dye Material), PD-311S (Yamamoto Chemicals, maximum absorption wavelength: 584 nanometers, porphyrin dye), SK-D593 (SK Chemicals, maximum absorption wavelength: 593 nanometers, vanadium dyestuff) and PANAX NEC595 (Uksung Chemicals, maximum suction At least one of receipts wavelength: 595 nanometers, mixture).

With solid content meter, content of the dyestuff in back coating composition can be 0.001wt% to 15wt%, especially 0.01wt% to 5wt%, more particularly 0.1wt% are to 3wt%.In the range, dyestuff can prevent fenestrated membrane from yellow is presented, together When prevent the transparency of fenestrated membrane from reducing.

Back coating composition can also include at least one of organic nanometer granule and simple inorganic particle.In back coating In composition, with solid content meter, the resin of the group containing ultraviolet curing relative to 100 parts by weight, organic nanometer granule and The amount of at least one of simple inorganic particle can be 0.1 parts by weight to 100 parts by weight, especially 1 parts by weight to 80 weight Part.In the range, back coating composition can have the surface roughness of reduction, and fenestrated membrane can have the pencil of increase Hardness.As used herein, term " simple particle " refers to non-hollow particle.

Back coating composition can also include any typical additive known in the art.Additive may include that ultraviolet light is inhaled Receive agent, reaction suppressor, adhesion promotor, thixotropic agent, conductivity imparting agent, color adaptation agent, stabilizer, antistatic agent, antioxygen At least one of agent and levelling agent.

Back coating composition may include solvent.The example of solvent may include isopropanol, glycol dimethyl ether, ethyl alcohol and Acetone.Preferably, solvent includes the mixture of isopropanol and glycol dimethyl ether.When the mixing of isopropanol and glycol dimethyl ether When object is used as solvent, the adhesiveness of base and back coating can be improved, can further decrease the yellowing of fenestrated membrane, and it is inorganic in Hollow particle can be better dispersed in back coating composition, to reduce the refractive index of back coating.

Back coating 130 can have 5 μm or smaller thickness, especially 300 nanometer or smaller, for example, 60 nanometers to 300 Nanometer, 100 nanometers to 300 nanometers or 150 nanometers to 300 nanometers.In the range, back coating can be used for fenestrated membrane, and can express Good flexibility out.

Fenestrated membrane can have 3H or higher pencil hardness, especially 3H to 8H.In the range, fenestrated membrane can be used for optics Display.Radius of curvature of the fenestrated membrane on compression direction can be 10.0 millimeters or smaller, especially 0.1 millimeter to 5.0 millimeters, And radius of curvature in the stretching direction can be 20.0 millimeters or smaller, especially 0.1 millimeter to 10.0 millimeters.At these In range, fenestrated membrane can have good flexibility, and therefore may be used as flexible fenestrated membrane.Due in compression and draw direction Radius of curvature all very littles, fenestrated membrane can have good flexibility in its two sides, and therefore can show good available Property.

Fenestrated membrane can have 50 μm to 300 μm of thickness.In the range, fenestrated membrane can be used for optical display.

Next, the fenestrated membrane by description according to another embodiment of the present invention.

It is substantially identical as according to the fenestrated membrane of above-described embodiment according to the fenestrated membrane of the present embodiment, in addition to back coating is by back coating Composition is formed, which includes inorganic hollow particle, fluorochemical monomer or its oligomer, fluorine-free monomer or its is oligomeric Object, initiator and solvent, wherein solvent includes weight ratio (unit: parts by weight) isopropanol and glycol dinitrate as described below Ether.

Back coating can be combined by the back coating including isopropanol (IPA) and the mixed solvent of glycol dimethyl ether (EGDE) Object is formed.In one embodiment, base can be polyimide film.Mixed solvent slightly dissolves the surface of polyimide film, To form buffer layer, to increase the adhesion strength of back coating and base, yellowing is further decreased, improves appearance, increases total light transmission Rate reduces reflectivity, and significantly reduces yellowing.In addition, mixed solvent improves inorganic hollow particle in back coating composition Dispersion, to reduce the refractive index of back coating.Based on the IPA and EGDE of 100 parts by weight in total, mixed solvent includes weight Than the IPA and EGDE for 80:20 to 50:50 (IPA:EGDE).In the range, mixed solvent can increase back coating and base Adhesion strength, improve appearance, increase total light transmittance, reduce reflectivity, and significantly reduce yellowing.If the weight of IPA and EGDE Than outside this range or the composition includes solvent in addition to the mixture of IPA and EGDE, for example, only IPA, ethyl alcohol, Acetone, acetonitrile or methyl iso-butyl ketone (MIBK) can then reduce the adhesion strength of back coating and base, and the reflectivity of fenestrated membrane can be very high, Iridescence can be generated in coating, and yellowing is caused to increase, the dispersion of inorganic hollow particle can be deteriorated, causes to generate pin hole, or The refractive index and yellowing of person's fenestrated membrane can be very high.

Next, the fenestrated membrane by reference Fig. 2 description according to another embodiment of the present invention.Fig. 2 is according to the present invention another The cross-sectional view of the fenestrated membrane of one embodiment.

With reference to Fig. 2, other than on the lower surface that adhesive phase 140 is further formed at back coating 130, according to the implementation The fenestrated membrane 200 and fenestrated membrane 100 according to the above embodiment of the present invention of example are essentially identical.Therefore, adhesive will be described mainly below Layer 140.

Adhesive phase 140 is formed on the lower surface of back coating 130, and fenestrated membrane 200 is allowed to be directly bonded to display Device, for example, polarizing film, conductive film and Organic Light Emitting Diode.Adhesive phase 140 can have 10 μm to 100 μm, especially It is the thickness of 20 μm to 80 μm, more particularly 30 μm to 50 μm.

In one embodiment, adhesive phase 140 can be by including (methyl) Acrylic Binder Resin and curing agent Adhesive phase composition is formed.(methyl) Acrylic Binder Resin may include (methyl) acrylic acid copolymer of monomer mixture Object, the monomer mixture include (methyl) acrylic monomers containing alkyl, (methyl) acrylic monomers of hydroxyl, containing alcyl (methyl) acrylic monomers, in (methyl) acrylic monomers containing heteroalicyclyl and (methyl) acrylic monomers containing carboxylic acid group At least one.

(methyl) acrylic monomers containing alkyl may include unsubstituted containing C₁To C₁₀(methyl) acrylate of alkyl. (methyl) acrylic monomers of hydroxyl may include at least one hydroxyl containing C₁To C₁₀(methyl) acrylic acid of alkyl Ester.(methyl) acrylic monomers containing alicyclic group may include containing C₃To C₁₀(methyl) acrylate of alicyclic group. (methyl) acrylic monomers containing heteroalicyclic group may include have at least one of nitrogen, oxygen and sulphur containing C₃To C₁₀Heterolipid (methyl) acrylic monomers of ring race group.(methyl) acrylic monomers of carboxy-containing acid group may include (methyl) acrylic acid Deng.Curing agent may include in isocyanate curing agent, epoxy hardener, acid imide curing agent and metal-chelating curing agent extremely Few one kind.These may be used alone or in combination.(methyl) acrylic acid with solid content meter, relative to 100 parts by weight Adhesive resin, amount of the curing agent in adhesive phase composition can be 0.1 parts by weight to 10 parts by weight, especially 0.1 weight Part is measured to 1 parts by weight.Adhesive phase composition can also include silane coupling agent.Silane coupling agent can be further improved bonding The adhesiveness of oxidant layer composition.Silane coupling agent may include at least one typical silane coupling agent.Specifically, silane coupled Agent may include the silane compound with epoxy construction, for example, 3- glycidoxypropyl trimethoxy silane, 3- shrink are sweet Oily oxygen propyl group methyl dimethoxysilane and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane；Containing polymerizable unsaturation The silane compound of group, for example, vinyltrimethoxysilane, vinyltriethoxysilane and (methyl) propenyloxy group third Base trimethoxy silane；And amino-containing silane compound, for example, 3- TSL 8330,3- aminopropyl Triethoxysilane, N- (2- amino-ethyl) -3- TSL 8330 and N- (2- amino-ethyl) -3- aminopropyl At least one of methyl dimethoxysilane.In adhesive phase composition, with solid content meter, relative to 100 parts by weight (methyl) Acrylic Binder Resin, the amount of silane coupling agent can be 0 parts by weight to 10 parts by weight, especially 0 parts by weight To 1 parts by weight.In the range, adhesive phase composition can have good adhesiveness.

In another embodiment, adhesive phase 140 can be formed by above-mentioned OCA.

Next, the method according to the present invention for preparing fenestrated membrane will be described.The method packet according to the present invention for preparing fenestrated membrane It includes and forms back coating on a surface of base using back coating composition, and using window coating composition in base Window coating is formed on another surface, wherein back coating composition may include inorganic hollow particle, fluorochemical monomer or its is oligomeric Object, fluorine-free monomer or its oligomer, initiator, dyestuff and solvent.It is preferably based on the IPA and EGDE of 100 parts by weight in total, Mixed solvent includes the IPA and EGDE that weight ratio is 80:20 to 50:50 (IPA:EGDE).Window coating can be by base The other side on coated window coating composition, then solidification to be formed.Back coating can be by a surface of base Back coating composition is coated, then solidification is to form.Back coating composition, window coating composition and base are same as described above.

In window coating composition and back coating composition each can by stick painting, spin coating, dip-coating, roller coating, Flow coat or die coating are coated in base, but not limited to this.It can be consolidated by least one of photocuring and heat cure Change.Can by under about 400 nanometers or smaller wavelength with 10mJ/cm²To 1000mJ/cm²Fluence under ultraviolet light Irradiation is to carry out photocuring.Heat cure can carry out 1 to 30 hour at 40 DEG C to 200 DEG C.Under these conditions, window coating Each in composition and back coating composition can sufficiently solidify.For example, heat cure can be carried out after photocuring, To obtain the more high rigidity of each coating.Solidifying the window coating composition and back coating composition being coated in base Before, window coating composition and back coating composition can be subjected to drying.In this way, can prevent due to long-term photocuring or heat Solidify and the surface roughness of each coating is caused to increase.Drying can carry out 1 minute to 30 hours at 40 DEG C to 200 DEG C, But not limited to this.

Next, flexible display according to an embodiment of the invention will be described with reference to Fig. 3 and Fig. 4.Fig. 3 is basis The cross-sectional view of the flexible display of one embodiment of the present of invention, Fig. 4 are cuing open for one embodiment of display portion shown in Fig. 3 View.

With reference to Fig. 3, flexible display 300 according to an embodiment of the invention includes display portion 350a, adhesive layer 360, polarizing film 370, touch screen panel 380 and flexible fenestrated membrane 390, wherein flexible fenestrated membrane 390 may include according to the present invention The fenestrated membrane of embodiment.

Display portion 350a may include the light of substrate and formation on substrate for driving flexible display 300 Device is learned, and the Optical devices include OLED, LED or LCD device.Fig. 4 is one embodiment of display portion shown in Fig. 3 Cross-sectional view.With reference to Fig. 4, display portion 350a may include lower substrate 310, thin film transistor (TFT) 316, Organic Light Emitting Diode 315, planarization layer 314, protective layer 318 and insulating layer 317.

Lower substrate 310 supports display portion 350a, and thin film transistor (TFT) 316 and Organic Light Emitting Diode 315 can be with shapes At on lower substrate 310.Lower substrate 310 could be formed with the flexible printed circuit board for driving touch screen panel 380 (FPCB).Flexible printed circuit board can also include time controller, power supply etc., to drive organic LED array.

Lower substrate 310 may include the substrate formed by flexible resin.Specifically, lower substrate 310 may include flexible liner Bottom, for example, silicon substrate, polyimide substrate, polycarbonate substrate and polyacrylate substrate, but not limited to this.

In the display area of lower substrate 310, multiple pixel domains are by a plurality of driving line (not shown) intersected with each other and more Pickup wire (not shown) limits, and each includes thin film transistor (TFT) 316 and the organic hair for being connected to thin film transistor (TFT) 316 The organic LED array of optical diode 315 can be formed in each pixel domain.In the non-display area of lower substrate, Gate drivers can take the form of grid in panel, to apply electrical signals to driving line.Grid circuit can be in panel It is formed in the one or both sides of display area.

Thin film transistor (TFT) 316 controls the electric current for flowing through semiconductor by applying the electric field perpendicular to semiconductor, and can To be formed on lower substrate 310.Thin film transistor (TFT) 316 may include gate electrode 310a, gate insulation layer 311, semiconductor layer 312, Source electrode 313a and drain electrode 313b.Thin film transistor (TFT) 316 can be using oxide (for example, indium gallium zinc oxide (IGZO), ZnO or TiO) as semiconductor layer 312 oxide thin film transistor, use organic material as the organic film of semiconductor layer Transistor uses amorphous silicon as the amorphous silicon film transistor of semiconductor layer or the polycrystalline for using polysilicon as semiconductor layer Silicon thin film transistor.

Planarization layer 314 covers thin film transistor (TFT) 316 and circuit 310b, to planarize thin film transistor (TFT) 316 and circuit The upper surface of 310b is formed thereon Organic Light Emitting Diode 315.Planarization layer 314 can be by spin-coating glass (SOG) film, polyimide polymer or acrylic acid polymer are formed, but not limited to this.

Organic Light Emitting Diode 315 is realized by spontaneous emission and is shown, and may include first stacked with the sequence Electrode 315a, organic luminous layer 315b and second electrode 315c.Adjacent Organic Light Emitting Diode can by insulating layer 317 that This isolation.Organic Light Emitting Diode 315 can have bottom-emission structure, wherein the light from organic luminous layer 315b passes through Lower substrate electric discharge, or can have top emission structure, wherein the light from organic luminous layer 315b is put by upper substrate Electricity.

Protective film 318 covers Organic Light Emitting Diode 315, to protect Organic Light Emitting Diode 315.Protective film 318 can be with It is formed by inorganic material, for example, SiO_x、SiN_x, SiC, SiON, SiONC and amorphous carbon (a-C), or by organic material shape At for example, (methyl) acrylate, epoxy polymer and imide polymer.Specifically, protective layer 318 may include encapsulation Layer, wherein inorganic material layer and organic material layer stack gradually one or many.

Referring again to FIGS. 3, display portion 350a is attached to polarizing film 370 by adhesive phase 360, and can be by including (methyl) acrylate, curing agent, initiator and silane coupling agent adhesive composition formed.

Polarizing film 30 may be implemented the polarization of interior lights or prevent the reflection of exterior light, to realize display, or can be with Increase the contrast of display.Polarizing film can be only made of polarizer.Alternatively, polarizing film may include polarizer and be formed in partially The protective film to shake on one or two surface of device.Alternatively, polarizing film may include polarizer and be formed in one of polarizer Or the protective coating on two surfaces.As polarizer, protective film and protective coating, can be used known in the art typical inclined Vibration device, typical protective film and typical protective coating.

When human body or conductor (for example, stylus) contact touch screen panel, touch screen panel 380 passes through detection capacitance variations Generate electric signal, and display portion 350a can be driven by this electric signal.Touch screen panel 380 passes through patterned flexible Conductor is formed, and may include first sensor electrode and second sensor electrode, and each sensor electrode is formed in Intersect between one sensor electrode and with first sensor electrode.Touch screen panel 380 may include conductive material, for example, golden Belong to nano wire, conducting polymer and carbon nanotube, but not limited to this.

The outermost in flexible display 300 can be set in fenestrated membrane 390, to protect flexible display.

Although being not shown in Fig. 3, adhesive phase can be further formed at polarizing film 370 and touch screen panel Between 380 and/or between touch screen panel 380 and flexible fenestrated membrane 390, to enhance between polarizing film, touch screen panel and fenestrated membrane Coupling.Adhesive phase can by include (methyl) acrylate, curing agent, initiator and silane coupling agent adhesive Composition is formed.Although being not shown in Fig. 3, polarizing film can be further disposed at below display portion 350a, with reality The polarization of existing interior lights.

Next, the flexible display by reference Fig. 5 description according to another embodiment of the present invention.Fig. 5 is according to this hair The cross-sectional view of the flexible display of bright another embodiment.

With reference to Fig. 5, flexible display 400 includes display portion 350a, touch screen panel 380, partially according to this embodiment Shake piece 370 and flexible fenestrated membrane 390, wherein fenestrated membrane 390 may include the fenestrated membrane of embodiment according to the present invention.In addition to touch screen Panel 380 is formed directly on display portion 350a, flexible display 400 substantially with the Flexible Displays according to above-described embodiment Device is identical.In addition, touch screen panel 380 can be formed together with display portion 350a.In this case, because of touch screen panel Plate 380 and display portion 350a are formed together on display portion 350a, so flexible display compares root according to this embodiment It is thinner and brighter according to the flexible display of above-described embodiment, to provide preferably visual.Furthermore, it is possible to by deposition, shape At touch screen panel 380, but not limited to this.

Although being not shown in Fig. 5, adhesive layer can be further formed at display portion 350a and touch screen panel 380 Between, between touch screen panel 380 and polarizing film 370 and/or between polarizing film 370 and fenestrated membrane 390, to enhance the machine of display Tool intensity.Adhesive phase can by include (methyl) acrylate, curing agent, initiator and silane coupling agent adhesive Composition is formed.In addition, polarizing film can be further disposed at below display portion 350a although being not shown in Fig. 5, with Good display image is provided by the polarization of interior lights.

Next, the flexible display by reference Fig. 6 description according to another embodiment of the present invention.Fig. 6 is according to this hair The cross-sectional view of the flexible display of bright another embodiment.

With reference to Fig. 6, flexible display 500 includes display portion 350b, adhesive layer 360 and flexible window according to this embodiment Film 390, wherein fenestrated membrane 390 may include the fenestrated membrane of embodiment according to the present invention.In addition to flexible display 500 can be independent Driven using display portion 350b and do not include except polarizing film and touch screen panel, flexible display 500 substantially with It is identical according to the flexible display of above-described embodiment.

Display portion 350b may include substrate and be formed on substrate and be filled including OLED, LED or the optics of LCD device It sets.Display portion 350b can also include touch screen panel wherein.

Although fenestrated membrane according to the embodiment is shown as being applied to flexible display, but it is to be understood that according to embodiment Flexible fenestrated membrane also can be applied to inflexibility display.

Next, some examples will be referred to, the present invention will be described in more detail.It should be appreciated that these embodiments are used for the purpose of Illustrate and provide, the limitation present invention can not be construed in any way.

Prepare example 1: back coating composition

By floride-free acrylic acid oligomer (UP118, ENTIS Co., Ltd, six functionalized propylene's acid oligomers) and no fluoropropene Acid monomers (SR9020, SARTOMER company, trifunctional acrylic monomers) contain inorganic hollow particle and fluoro-acrylate monomer Solution (XJA-0247, PELNOX company, the content of inorganic hollow particle and fluoro-acrylate monomer: 10wt%), initiator (Irgacure 184, BASF) and dyestuff (SK-D593, SK Chemicals) mixing, so that floride-free acrylic acid oligomer, free-floride Acrylic monomers, entire inorganic hollow particle and fluoro-acrylate monomer, initiator and dyestuff are respectively provided with shown in the table 1 Amount, and isopropanol (IPA) and glycol dimethyl ether (EGDE) are then added into mixture (weight ratio of IPA and EGDE is Mixed solvent 7:3) is subsequently agitated for 30 minutes, thus prepares back coating composition.

Prepare example 2 to 16: back coating composition

In addition to using floride-free acrylic acid oligomer (UP118), floride-free acrylic monomers (SR9020), containing inorganic hollow Except the solution (XJA-0247) of grain and fluoro-acrylate monomer, initiator (Irgacure 184) and dyestuff (SK-D593), with Back coating composition is prepared with the identical mode of preparation example 1, so that floride-free acrylic acid oligomer, floride-free acrylic monomers, whole A inorganic hollow particle and fluoro-acrylate monomer, initiator and dyestuff change as shown in table 1.

Prepare example 17: window coating composition

By 50 grams of 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane (KBM-303, Shin-Etsu Chemical) It is put into 200 milliliter of 3 neck flask.Then, it is based on the amount of 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, is added The water of the KOH and 1.5mol% of 0.5mol% are then stirred 1 hour at 25 DEG C and are stirred 2 hours at 70 DEG C.Then, using true Empty distiller removes remaining solvent from products therefrom, so that silicone resin is prepared, with solid content meter, silicone resin It is adjusted to 90wt% again.It is measured by gel permeation chromatography (GPC), the weight average molecular weight of silicone resin is 5,000g/ mol.Standby silicone resin and 15 grams of 3,4- epoxycyclohexyl-methyl 3', 4'- epoxies as curable monomer are restrained by 100 Hexahydrobenzoid acid ester (CY-179, CIBA Co., Ltd), 2 grams of diphenyl iodine hexafluorophosphate (Sigma as initiator Aldrich Co., Ltd) and 60 grams of methyl ethyl ketone mixing, to prepare window coating composition.

Table 1

1.: floride-free acrylic acid oligomer

2.: floride-free acrylic monomers

3.: inorganic hollow particle and fluoro-acrylate monomer

4.: initiator

5.: dyestuff

IPA: isopropanol

EGDE: glycol dimethyl ether

EtOH: ethyl alcohol

Acetone

MIBK: methyl iso-butyl ketone (MIBK)

ACN: acetonitrile

Example 1

The back coating composition prepared in example 1, which will be prepared, using bar coater is coated to transparent polyimide film (thickness Degree: 75 μm, yellow colour index: 3.2) on a surface, then dry 3 minutes in 80 DEG C of baking ovens, and under nitrogen atmosphere with 300mJ/cm²Fluence carry out ultraviolet light irradiation, thus in transparent polyimide film formed back coating (thickness: 100 μ m)。

Transparent polyimide film is coated to by the window coating composition prepared in example 17 is prepared using bar coater Another surface on.Then, the composition of coating is 3 minutes dry in 80 DEG C of baking oven, under nitrogen atmosphere with 500mJ/cm² Fluence be exposed to ultraviolet light, and at 120 DEG C after solidification 24 hours, to prepare fenestrated membrane, wherein shape according to the sequence At window coating (thickness: 50 μm), transparent polyimide film (thickness: 75 μm) and back coating (thickness: 100nm).

Example 2 to 14

In addition to use the back coating composition listed in table 2 replace preparation example 1 back coating composition other than, with show The identical mode of example 1 prepares fenestrated membrane.

Comparative example 1 to 2

The performance of the every kind of fenestrated membrane prepared in example and comparative example is evaluated, as shown in table 2.

(1) it refractive index: when measuring the refractive index for the base that wavelength is 550 nanometers, uses ellipsometer (J.A.Woollam) Under 400 nanometers to 800 nanometers of wavelength, the base of each fenestrated membrane prepared in example and comparative example is measured.? When measuring the refractive index for the window coating that wavelength is 550 nanometers, received using ellipsometer (J.A.Woollam) at 400 nanometers to 800 Rice wavelength under, the window coating of each fenestrated membrane prepared in example and comparative example is measured, wherein using sand paper from Middle removal back coating.When measuring the refractive index for the back coating that wavelength is 550 nanometers, existed using ellipsometer (J.A.Woollam) Under 400 nanometers to 800 nanometers of wavelength, the back coating of each fenestrated membrane prepared in example and comparative example is measured, In, window coating is therefrom removed using sand paper.

(2) it total light transmittance and mist degree: is received using haze meter (NDH2000, NIPPON DENSHOKU) at 400 nanometers to 800 Under the wavelength of rice, to each fenestrated membrane measurement total light transmittance and mist degree prepared in example and comparative example.

(3) reflectivity: every to being prepared in example and comparative example according to the standard of ASTM E1164 and JIS Z 8722 A fenestrated membrane measures reflectivity.Specifically, using spectrophotometer (CM-3600A, KONICA MINOLTA) at 400 nanometers to 800 It is measured under the wavelength of nanometer.

(4) pencil hardness: firstly, each fenestrated membrane prepared in example and comparative example is cut into having a size of 50mm × The sample of 50mm (width x length), and pencil hardness tester (Heidon-14EW, SHINTO are then used according to JIS K5400 SCIENTIPIC Co., Ltd) pencil hardness is measured to the window coating of sample.Here, using the pencil of 6B to 9H (Mitsubishi Co., Ltd).Specifically, it measures under the following conditions: the scraping speed of 60mm/min, 19.6N Power, 45 ° of scraping angle, the load of 1kg and 10.0 millimeters of scale.When coating is had after being tested 5 times using certain pencil When having one or more scrape, it is hard that pencil is measured again using another pencil of pencil hardness level-one lower than previous branch pencil Degree.Permission observes that the Pencil Hardness values of not scratch are considered as the pencil hardness of coating whole 5 times on coating.

(5) radius of curvature: firstly, being cut into each fenestrated membrane prepared in example and comparative example having a size of 3 cm x The sample of 15 centimetres (width x length), and then sample is wrapped on fixture, for measuring radius of curvature (bent spindle test Instrument, COVOTECH Co., Ltd), winding 5 seconds, expansion are kept, and then detect by an unaided eye, is split with determining whether sample has Line.When measuring the radius of curvature on compression direction, sample is wrapped on fixture, so that window coating is contacted with fixture.It is surveying When measuring the radius of curvature on draw direction, sample is wrapped on fixture, so that back coating or base contact with fixture.Radius of curvature It is determined by the least radius of fixture, crackle will not be caused in the sample, be gradually reduced since the fixture with maximum gauge It is measured while the diameter of fixture.

(6) yellow colour index: according to ASTM D1925, each fenestrated membrane measurement yellow prepared in example and comparative example is referred to Number.In the measurements, using spectrophotometer (CM-3600A, KONICA MINOLTA).Specifically, at 360 nanometers to 740 nanometers Wave-length coverage in, measured with 10 nanometers of wavelength interval, and the measurement diameter of sample be 25.4 millimeters.In addition, making For light source, using D65 lamp, and the light from lamp travels to window coating from back coating.

Table 2

*A¹: the refractive index of back coating, A²: the refractive index of window coating, A³: the refractive index of base

The result shown in the table 2 can be seen that exemplary fenestrated membrane according to the present invention with high total light transmittance, ground fog Degree, antiradar reflectivity and low yellowing.

On the contrary, the fenestrated membrane of the comparative example 1 and 2 without inorganic hollow particle and fluorochemical monomer has compared with those examples There are lower total light transmittance and higher reflectivity.

It should be appreciated that without departing from the spirit and scope of the present invention, those skilled in the art can carry out respectively Kind modification, change, change and equivalent embodiment.

Claims

1. a kind of fenestrated membrane, comprising:

Base；Window coating is formed on a surface of the base；And back coating, it is formed in the another of the base On surface,

Wherein, the fenestrated membrane meets equation 1:

A¹<A²<A³

(wherein, A¹It is the refractive index of the back coating, A²It is the refractive index of the window coating, and A³It is the folding of the base Penetrate rate).

2. fenestrated membrane according to claim 1, wherein the back coating has 1.54 or smaller refractive index, the window Coating has the refractive index less than 1.60, and the base has 1.60 or bigger refractive index.

3. fenestrated membrane according to claim 1, wherein the base includes polyimide film.

4. fenestrated membrane according to claim 1, wherein the window coating is by the window coating composition shape comprising silicone resin At.

5. fenestrated membrane according to claim 1, wherein the back coating includes at least one in fluorochemical monomer and its oligomer Kind, inorganic hollow particle and dyestuff.

6. fenestrated membrane according to claim 5, wherein the inorganic hollow particle includes hollow silica.

7. fenestrated membrane according to claim 1, wherein the back coating is formed by back coating composition, the back coating group Closing object includes: inorganic hollow particle；At least one of fluorochemical monomer and its oligomer；In fluorine-free monomer and its oligomer extremely Few one kind；Initiator；And dyestuff.

8. fenestrated membrane according to claim 7, wherein with solid content meter, the back coating composition include 9wt% extremely The inorganic hollow particle and fluorochemical monomer or its oligomer of 80wt%, 15wt% to the fluorine-free monomer of 88wt% or its oligomer, The initiator and 0.001wt% of 1wt% to 5wt% to 15wt% dyestuff.

9. fenestrated membrane according to claim 7, wherein the back coating composition further includes solvent, and the solvent is isopropyl The mixed solvent of pure and mild glycol dimethyl ether.

10. fenestrated membrane according to claim 9, wherein the mixed solvent includes isopropanol and glycol dimethyl ether, is based on The weight ratio of the isopropanol and glycol dimethyl ether of 100 parts by weight, isopropanol and glycol dimethyl ether is 80:20 to 50:50.

11. fenestrated membrane according to claim 1, wherein the fenestrated membrane has 90% or bigger total light transmittance and 8% or more Small reflectivity.

12. fenestrated membrane according to claim 1, wherein the base is polyimide film, and the fenestrated membrane has 2.3 Or smaller yellow colour index.

13. fenestrated membrane according to claim 1, wherein the base has 10 μm to 150 μm of thickness, and the window applies Layer has 5 μm to 100 μm of thickness, and the back coating has the thickness of 150nm to 300nm.

14. fenestrated membrane according to claim 1, wherein the back coating further includes dyestuff.

15. fenestrated membrane according to claim 1, wherein the back coating further include ultraviolet absorbing agent, reaction suppressor, In adhesion promotor, thixotropic agent, conductivity imparting agent, color adaptation agent, stabilizer, antistatic agent, antioxidant and levelling agent It is at least one.

16. fenestrated membrane according to claim 1, further includes:

The adhesive phase being formed on a surface of the back coating.

17. fenestrated membrane according to claim 1, wherein the base includes film lamination, wherein the first base, adhesive phase It is stacked gradually with the second base.

18. a kind of method for preparing fenestrated membrane, comprising:

Back coating is formed on a surface of base using back coating composition；And

Window coating is formed on another surface of the base using window coating composition,

Wherein, the back coating composition includes: inorganic hollow particle；At least one of fluorochemical monomer and its oligomer；Nothing At least one of fluorine monomer and its oligomer；Initiator；Dyestuff；And solvent.

19. according to the method for claim 18, wherein the inorganic hollow particle is hollow silica, and described Window coating composition includes silicone resin.

20. according to the method for claim 18, wherein the solvent is the mixing comprising isopropanol and glycol dimethyl ether The weight ratio of solvent, isopropanol and glycol dimethyl ether based on 100 parts by weight, isopropanol and glycol dimethyl ether is 80:20 To 50:50.

21. a kind of flexible display, including according to claim 1 to fenestrated membrane described in any one of 17.